Dyestuffs of the anthrimide series



Patented Oct. 11, 1938 DYESTUFFS OF 2,133,072 7 I THE ANTHRIMIDE SERIESv w Earl E. Beard, South Milwaukee, Wis., assignor to E. I. du Pont deNemours & Company, Wil

mington, DeL, a. corporation of Delaware No Drawing. Application April22,137,;

SerialNo. 138,315 '3 Claims. o1. "zoo-i368) This invention relates tothe preparation off, bonylimino-'-aminoanthraquinone, 25 parts ofTZ-clilorotinthraquinone, 0.5 part of basic copper acetate and 12 partsof soda ash are mixed in new and valuable ,dyestufis of the anthrimideseries, and has for its object-the preparationfofaz:

new alpha-beta-anthrimides containing the nu- 5 icleus of I1-aminoanthraquinone#6-carboxylic acid, which dye and print in red-brownshades of excellent fastness properties.

While a nu'rnber of the'alpha-beta type an-' thrimide'compounds havebeen prepared, it is recognized that in the main they are usedcommercially only for dyeing; since most of these products exhibit poorprinting properties.

I have found that by combining beta'-halogen-anthraquinones withl-aminoanthraquinone-G-carboxylic acid substituted infthe acid radicalby an arylamine group, anthrimide dyestuffs are obtained which dye inred-browns shades and which can be used for either dyeing carboxylicacid may be of the benzene or an-'.

thraquinone series including the higher ring con- 25 densation pro-ductsof anthraquinone. 'While. the

' general condensation reaction employed in the preparation of thesecompounds is not itself.

new, it has been found that where the l-amino anthraquinone-6-carboxylioacid] nucleus 1 is introduced into the anthriinide -mo1cu1e,by,c0ndensing the same with a beta-halogen-anthraquinone compounddesirable dyestufis are obtained which dye cellulose fibers in red=brownshades, and that/the printing properties of these new dyes aresuperiorto those ordinarily obtained by the: condensation ofalphaaminoanthraquinones with beta halogen anthraguinones. The followingexamples are given to"more' 4 fully illustrate a method for preparingthese new dyestufis. The parts used are by weight.

' Example 1 7 parts of l amino-j6 anthraquinonecarboxylic acid anilideare heated with 3 parts of anhydrous sodium acetate, 0.5 part of copperacetate, 52 parts of 2-chloroanthraquinone and 100, parts ofnitrobenzene at 200 to 206. C. for 12 hours. The reaction mixture iscooled to 80 C., diluted in solvent naphtha, filtered and washed with 50solvent naphtha, alcohol, and water, in turn.

The alpha-beta-dianthrimide thus obtained gives a bright bluish greencolor in sulfuric acid and dyes cotton in reddish brown shades from adarkreddish brown vat. V Y 1 benzoylamino 6 chloroanthraquinone may beSubstituted for the 2-ch1or0anthraqum0n 1? i ole 1 benzoy]amino ficmoroanthraqui used in this example. i

Example 2 24 parts of l-aminoanthraquinonyl-6,1'- car-.-

compound is a brownish red solid giving a yellowishgreen color insulfuric acid. 'It can be used without further purification fordyeing orprinting in red-brown shades. If desired, it"can be purified bydichromating in dilute sulfuric acid or bybIeachingwith sodiumhypochlorite.

Emample 'v i 10 parts of 1-aminoanthraquinonyl-,l'-carbonylimino-5'-aminoanthraquinone are condensed with 15.5. parts of1-benzoyl'arnino-6 chloroanthraquinone and'150 parts of nitrobenzene inthe presence of 5 parts of anhydrous sodium acetatand 0.5 part of copperacetate.

1 The-condensation is complete after 12 hoursat 200 to 206 C. Theproduct is isolated bythe method disclosed in Example land gives abright blue"'-color in sulfuric acid. It dyes cotton in very reddishbrown shades from a dark reddish brown vat and shows excellenttinctorial strength.

Example 4 By the same procedure described'in the above examples 1 moleof2-chloroanthraquinone may be condensed with 1-aminoanthraquinonyl-6,1-carbonylimino 5 behzoylaminoanthraquinone' to give a compound having thefollowingformula v r 1 Nil-000.11, which gives an olive green sulfuricacid solution color and dyes cotto nin'red-brown shades.

' Example 5 none is condensed with 1 mole ofl-aminoanthr'aquinonyl-6,1'- carbonylimino 5'- benzoylaminoanthraquinoneby the procedure described in the above examples and gives a producthaving the following general formula oemoo mi o which, gives; a bluecolor in sulfuric acid and dyes cotton in red-brown shades.

Example 6 1 mole of 2 ,fi dichloroanthraquinone condensed with 2 molesof l-aminoanthraquinonyl-6,1f-carbonylimino-S-benzoylaminoanthraquinoneby the process described above gives a product having the followinggeneral formula CgHaQO-NE o I O NEE-G0 vvhichgives an olive-brown colorinrsulfuric acid and dyes cotton in red-brownshades.

I Example 7- 7 On condensation of 1 mole of 2-chloroanthraquinone with 1mole of l-aminoanthraquinonyl- 6.5-carbonyliminoanthraquinone-2' ,1 (N)-benz-v acridone by the procedure describedin the above examples, aproduct is obtained which has the following general formula which givesa yellow-brown color in sulfuric acid and dyes cotton in red-brownshades.

In place of the 2-chloroanthraquinones used in the above examples, the2-bromo compounds may be employed and the condensation of thebeta-halogen-anthraquinones with the alphaaminoanthraquinone compoundsmay be effected byany of the processes generally employed in thepreparation of anthrimide compounds.

V v L- 1 0 'I'he- 1 amino-rfi:anthraquinonecarbonylaminoaryl compoundsmay be'preparedby. condensing arylamino compounds with l-nitroanthraquinone-G-carbonyl halides, asdescribed' in U. S. Patent 2,001,701, withsubsequent reduction of the nitro group to the corresponding amine, asde I scribed in U. S. Patent 2,001,702; V

What I claim is: I 1. Compounds of the formula Aq-NH 7 o (Lint-R whereinAq stainds for-an anthraquinonegi'oup attached to the imino radical inthe beta. position and R stands for an aromaticradicalof the classconsisting of those of the benzene'and the anthraquinone series; 7

2. The compounds ot'the formula.

"tom

wherein Aq and Aq stand for anthraqulnone groups and wherein Aq isattached to the imino linkage in the beta position. r

'3. The compound of the formula EARL E. BEARD.

